Optical high-pressure experiments

Even though the rates of initiation span almost a 10-fold range, the values of k, show a standard deviation of only 4%, which is excellent in view of experimental errors. Note that the rotating sector method can be used in high-pressure experiments and other unusual situations, a characteristic it shares with many optical methods in chemistry. 

Semiconducting properties of BP have been clarified to some extent. Theoretical band calculations yield very useful information so that optical properties of BP should be clarified by comparing calculation with experimental data. Theoretical band calculations also indicate that the fundamental gap in BP decreases with increasing pressure (12,79) as in most ni-V compound semiconductors, which should be confirmed by high-pressure experiment. 

Quednau J and Schneider G M 1989 A new high-pressure cell for differential pressure-jump experiments using optical detection Rev. Sc/. Instnim. 60 3685-7... 

A schematic diagram of the apparatus used in the energy transfer experiments is shown in Figure 8.22. The particles are produced and levitated in an electrodynamic levitator as described previously. Excitation is provided by the filtered output of either a Xe or Hg-Xe high-pressure arc. The intensity produced at the particle was found to be 10-50 mW/cm2. The fluorescence emitted from each of the levitated particles was monitored at 90° to the exciting beam using //3 optics, dispersed with a j-m monochromator, and detected with an optical multichannel analyzer. The levitator could be... 

It should be recognized that the exponential expressions in eqs. (17) and (18) are simply correction terms designed to normalize rates observed in solutions not optically black to the limiting rates for optically black solutions (i.e., the rate independent of pyrimidine concentration), and have no other kinetic importance. Such extrapolations as shown in this footnote are hazardous for most experiments using ordinary medium pressure or high pressure (i.e., sources with continuum and not simply line emission). It is likely that some of the other variations in quantum yield with concentration mentioned here and in ref. 7 are also artifacts. 

The NEXAFS experiments reported here were carried out at the U1 Beamline of the National Synchrotron Light Source, Brookhaven National Laboratory. Details concerning the optics of the beamline, as well as the UHV chamber with facilities for high pressure reactions, have been described previously.7,8 In our experimental set-up, NEXAFS spectra can be recorded by measuring either the electron yield or fluorescence yield. While the electron yield method is sensitive only to the top few atomic... 

The high-pressure cells and temperature control units are similar to the ones described by Betts and Bright (29). Samples for analysis were prepared by directly pipetting the appropriate amount of stock solution into the cell. To remove residual alcohol solvent, the optical cell was placed in a heated oven (60 °C) for several hrs. The cell was then removed from the oven, connected to the high-pressure pumping system (29), and a vacuum (50 pm Hg) maintained on the entire system for 10-15 minutes. The system was then charged with CF3H and pressurized to the desired value with the pump (Isco, model SFC-500). Typically, we performed experiments at 10 /xM PRODAN and there was no evidence for primary or secondary interfilter effects. HPLC analysis of PRODAN subjected to supercritical solvents showed no evidence of decomposition or additional components. 

In view of the small sample size, the optical aperture used for pressure tuning vibrational spectroscopic measurements is also very small. This does not create serious problems for high pressure Raman spectroscopic measurements since the laser beam can be focused to 30-40 pm. Thus, the optical system employed in a standard Raman scattering experiment can be used and no special optical interface is required for the pressure tuning Raman spectroscopic measurements. 

In contrast to what is known about a-Si, much less is understood about polyamorphism in Ge. The authors of most early experiments reported no direct evidence of LDA-HDA transition in Ge [260-262, 270, 271]. Shimomura et al. [260] observed a stepwise drop of the electronic resistance (at 6 and lOGPa) after compression of an -Ge him. This decrease, however, may have resulted from (partial) recrystallization to a metallic high-pressure polymorph under pressure. Tanaka [270] measured X-ray diffraction patterns and optical absorption spectra of -Ge at pressures up to lOGPa. In this experiment, the sample was indeed partly transformed to the (3-tin crystalline phase ( 25% in volume) at 6 GPa. Imai et al. [262] also observed an amorphous to [3-tin crystal transition. Freund et al. [271], in contrast, have observed no sign of crystallization or transition to an HDA form after compression up to 9 GPa. 

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